WO2015023714A2

WO2015023714A2 - Plasticizers comprising poly(trimethylene ether) glycol esters

Info

Publication number: WO2015023714A2
Application number: PCT/US2014/050800
Authority: WO
Inventors: Hari Babu Sunkara; Raja Hari Poladi; Herbert Vernon Bendler
Original assignee: E. I. Du Pont De Nemours And Company
Priority date: 2013-08-13
Filing date: 2014-08-13
Publication date: 2015-02-19
Also published as: WO2015023714A3; US20150051326A1

Abstract

Plasticizers comprising monoesters and/or diesters of poly(trimethylene ether) glycol are provided. The plasticizers can be used in plasticizing a variety of base polymers.

Description

CL6091

TITLE

PLASTICIZERS COMPRISING PQLY(TRi METHYLENE ETHER) GLYCOL

ESTERS

FIELD OF THE INVENTION This invention relates to piasticizers comprising monocarboxylic acid esters (monoesters and/or diesters) of poly(trimethylene ether) glycol and their use in plasticizing a variety of base polymers.

BACKGROUND

Piasticizers are substances which, when added to another material, make that material softer and more flexible. Generally, this means that there is an increase in flexibility and workability, in some cases brought about by a decrease in the glass-transition temperature, Tg, of the polymer. The polymer to which a plasticizer is added is generally referred to as a "base polymer". One base polymer that is commonly plasticized is polyfvinyl chloride) (PVC), and another polymer is polyvinyl butyral) (PVB).

Commonly-used piasticizers include phthalates, including, for example, diisobutyl phthaiate, dibutyl phthalate, and benylbutyl phthaiate; adipates, including di-2-ethylhexyi adipate; trimeiiitates, inciuding tris-2-ethyihexyl trimeliitate; and phosphates, including tri-e-ethylhexyl phosphate. However, the use of some of these have been curtailed due to potential toxicity issues.

Polyester piasticizers have also been used, but those have generally been based on condensation products of propanediol or butanediol with adipic acid or phthalic anhydride, and therefore may exhibit very high viscosities which subsequently cause processing problems in blending with other polymers. Plasticization of polymers is disclosed, for example, in D. F. Cadogan and C. J. Howick in Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley and Sons, Inc., New York, December 4, 2000, DOi:

10.1002/0471238961 .161201 1903010415.a01 . CL6091 USNA

Various monocarboxylic acid mono- and diesters of polytrimethy!ene ether glycol have properties that make them useful in a variety of fields, including as lubricants. U.S. Pat. Appl. No. 1 1/593954 discloses the production of these esters and their use in a variety of functional fluids. Epoxidized vegetable oils are also widely used piasticizers for PVC and other polymer matrices. These materials can provide low migration into adjoining materials, synergistic stabilizing and better low-temperature flexibility of the plasticized polymer material. Some of the epoxidized vegetable oils have been approved for use in food packaging applications, in the epoxidation process soybean oil and tali oil fatty acids used to react hydrogen peroxide and acetic acid in the presence of a catalyst and generates performic acid and other undesirable impurities. Generally, vegetable oils (as soybean oils, or refined grades of tall oil fatty acids) are a mixture of different saturated/unsaturated fatty acids; therefore, to manufacture esters with controlled structure and molecular weight is very difficult.

A need remains for processes and compositions for plasticizing polymers while minimizing impurities and improving properties of the polymers.

SUMMARY OF THE INVENTION

One aspect of the present invention is a polymer composition, comprising an effective amount of piasticizer in a base polymer, wherein the piasticizer comprises an ester of poly(trimethylene ether) glycol.

Another aspect of the present invention is a process for producing a plasticized polymer, comprising: a. providing a base polymer; b. adding to the base polymer an effective amount of a piasticizer, wherein the piasticizer comprises an ester of polyffrimethyiene ether) glycol; c. processing the base polymer and piasticizer to form a mixture; and CL6091 USNA

d. cooling the mixture.

In some embodiments, the processing of the base polymer and plasticizer comprises melt processing at a temperature from 20 to 40 °C above the melt temperature of the base polymer.

In some embodiments, the processing of the base polymer and plasticizer comprises forming an aqueous slurry or solvent (i.e., containing a non-aqueous solvent) slurry.

The mixture after processing and cooling can be ground to form particles.

Another aspect is a polymer composition, comprising an effective amount of plasticizer in an aliphatic polyamide base polymer, wherein the plasticizer comprises an aromatic ester of poiy(trimethyiene ether) glycol.

Another aspect is a process for producing a plasticized polymer, comprising:

(a) providing an aliphatic polyamide base polymer;

(b) adding to the base polymer an effective amount of a plasticizer, wherein the plasticizer comprises an aromatic ester of poly(trimethylene ether) glycol;

(c) processing the base polymer and plasticizer to form a mixture; and

(d) cooling the mixture and optionally grinding the mixture to produce particles.

Another aspect is a shaped article comprising the polymer composition, comprising an effective amount of plasticizer in an aliphatic polyamide base polymer, wherein the plasticizer comprises an aromatic ester of

poly(trimethylene ether) glycol CL6091 USNA

DETAILED DESCRIPTION Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, in case of conflict, the present specification, including definitions, will control.

Unless stated otherwise, all percentages, parts, ratios, etc., are by weight.

When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing ail ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and ail integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range. When the term "about" is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end- point referred to.

As used herein, the terms "comprises," "comprising," "includes,"

"including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated CL6091 USNA

to the contrary, "or" refers to an inclusive or and not to an exciusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). Use of "a" or "an" is employed to describe elements and components of the invention. This is done merely for convenience and to give a general sense of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise. The materials, methods, and examples herein are illustrative only and, except as specifically stated, are not intended to be limiting. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein. According to embodiments of the present invention, plasticizers comprising one or more esters (a monoester, a diester or mixtures thereof) of a polytrimethylene ether glycol are provided, in preferred embodiments, the plasticizers are prepared from renewably sourced ingredients. "Mixtures thereof, as used herein in connection with a list of components, e.g., polymers, is intended to encompass mixtures of any two or more of the listed

components, unless otherwise indicated.

The plasticizers are compositions comprising one or more compounds of the formula (I):

o

-OO-Q-O-R'

0) CL6091 USNA

wherein Q represents the residue of a po!y(trimethylene ether) glycol after abstraction of the hydroxy! groups, R² is H or R³CQ, and each of R¹ , and R³ is individually a substituted or unsubstituted aromatic, saturated aliphatic, unsaturated aliphatic, or cycloaliphatic organic group containing from 2 to 40 carbon atoms.

Poly(trimethylene ether) glycol esters are preferably prepared by polycondensation of hydroxy! groups-containing monomers (monomers containing 2 or more hydroxyl groups) predominantly comprising

1 ,3-propanedio! to form poly(trimethylene ether) glycol, followed by

esterification with a monocarboxyiic acid. The ester compositions preferably comprise from about 50 to 100 wt%, more preferably from about 75 to 100 wt%, diester and from 0 to about 50 wt%, more preferably from 0 to about 25 wt%, monoester, based on the total weight of the esters.

Polvftrimethviene ether) Glycol (PQ3G) Po!y(trimethy!ene ether) glycol for the purposes of the present disclosure is an oligomeric or polymeric ether glycol in which at least 50% of the repeating units are trimethylene ether units. More preferably from about 75% to 1 (30%, still more preferably from about 90% to 100%, and even more preferably from about 99% to 100%, of the repeating units are trimethylene ether units. Poiy(trimethy!ene ether) glycol is preferably prepared by

polycondensation of monomers comprising 1 ,3-propanedioi, thus resulting in polymers or copolymers containing -(CH₂CH₂CH₂O)- linkage (e.g, trimethylene ether repeating units). As indicated above, at least 50% of the repeating units are trimethylene ether units. in addition to the trimethylene ether units, lesser amounts of other units, such as other polyalkylene ether repeating units, may be present. In the context of this disclosure, the term "po!y(trimethy!ene ether) glycol" encompasses P03G made from essentially pure 1 ,3-propanedioi, as well as those oligomers and polymers (including those described below) containing up to about 50% by weight of comonomers. CL6091 USNA

The 1 ,3-propanediol employed for preparing the poly(trimetbylene ether) glycol may be obtained by any of the various well known chemical routes or by biochemical transformation routes. Preferred routes are described in, for example, US20050069997A1 . Preferably, the 1 ,3-propanediol is obtained biochemically from a renewable source ("biologically-derived" 1 ,3-propanediol).

A particularly preferred source of 1 ,3-propanediol is via a fermentation process using a renewable biological source. As an illustrative example of a starting material from a renewable source, biochemical routes to 1 ,3- propanediol (PDO) have been described that utilize feedstocks produced from biological and renewable resources such as com feed stock. For example, bacterial strains able to convert glycerol into 1 ,3-propanediol are found in the species Klebsiella, Citrobacter. Clostridium,, and Lactobacillus. US5821092 discloses, inter alia, a process for the biological production of 1 ,3-propanediol from glycerol using recombinant organisms. The process incorporates £. coli bacteria, transformed with a heterologous pdu diol dehydratase gene, having specificity for 1 ,2-propanedioL The transformed E. coli is grown in the presence of glycerol as a carbon source and 1 ,3-propanediol is isolated from the growth media. Since both bacteria and yeasts can convert glucose (e.g., corn sugar) or other carbohydrates to glycerol, the processes disclosed in these publications provide a rapid, inexpensive and environmentally responsible source of 1 ,3- propanediol monomer.

The biologically-derived 1 ,3-propanediol, such as produced by the processes described and referenced above, contains carbon from the atmospheric carbon dioxide incorporated by plants, which compose the feedstock for the production of the 1 ,3-propanediol. In this way, the biologically- derived 1 ,3-propanediol preferred for use in the context of the present invention contains only renewable carbon, and not fossil fuel-based or petroleum-based carbon. The P03G and esters based thereon utilizing the biologically-derived 1 ,3-propanediol, therefore, have less impact on the environment as the 1 ,3- propanediol used in the compositions does not deplete diminishing fossil fuels CL6091 USNA

and, upon degradation, releases carbon back to the atmosphere for use by plants once again. Thus, the compositions of the present invention can be characterized as more natural and having less environmental impact than similar compositions comprising petroleum based glycols. The biologically-derived 1 ,3-propanediol, P03G and P03G esters, may be distinguished from similar compounds produced from a petrochemical source or from fossil fuel carbon by dual carbon-isotopic finger printing. This method usefully distinguishes chemically-identical materials, and apportions carbon in the copolymer by source (and possibly year) of growth of the biospheric (plant) component. The isotopes, ⁴C and ¹³C, bring complementary information to this problem. The radiocarbon dating isotope (¹⁴C), with its nuclear half life of 5730 years, clearly allows one to apportion specimen carbon between fossil ("dead") and biospheric ("alive") feedstocks (Currie, L. A.

"Source Apportionment of Atmospheric Particles," Characterization of

Environmental Particles, J. Buffle and H.P. van Leeuwen, Eds., 1 of Vol. I of the iUPAC Environmental Analytical Chemistry Series (Lewis Publishers, Inc) (1992) 3-74). The basic assumption in radiocarbon dating is that the constancy of ⁴C concentration in the atmosphere leads to the constancy of ¹⁴C in living organisms. When dealing with an isolated sample, the age of a sample can be deduced approximately by the relationship: t - (-573070.693)ln(A/Ao) wherein t = age, 5730 years is the half-life of radiocarbon, and A and Ao are the specific ¹⁴C activity of the sample and of the modern standard, respectively (Hsieh, Y., Soil ScL Soc. Am J., 56, 460, (1992)). However, because of atmospheric nuclear testing since 1950 and the burning of fossil fuel since 1850, C has acquired a second, geochemical time characteristic. Its concentration in atmospheric CO₂, and hence in the living biosphere, approximately doubled at the peak of nuclear testing, in the mid-1960s. It has since been gradually returning to the steady-state cosmogenic (atmospheric) baseline isotope rate ( C/ ²C) of ca, 1 .2 x 10^"12, with an approximate relaxation "half-life" of 7-10 years. (This latter half-life must not be taken literally; rather, CL6091 USNA

one must use the detailed atmospheric nuclear input/decay function to trace the variation of atmospheric and biospheric ⁴C since the onset of the nuciear age.) it is this latter biospheric ¹⁴C time characteristic that holds out the promise of annual dating of recent biospheric carbon. ¹⁴C can be measured by accelerator mass spectrometry (A S), with results given in units of "fraction of modern carbon" ¾). fivi is defined by National Institute of Standards and Technology ( IST) Standard Reference Materials (SRMs) 4990B and 4990C, known as oxalic acids standards HOxl and HOxIL respectively. The fundamental definition relates to 0.95 times the ¹⁴C/ ²C isotope ratio HOxl (referenced to AD 1950). This is roughly equivalent to decay-corrected pre~lndustrial Revolution wood. For the current living biosphere (plant material), ff < ^«1 .1 .

The stable carbon isotope ratio ( C/¹²C) provides a complementary route to source discrimination and apportionment. The ^|3C/ ²C ratio in a given biosourced material is a consequence of the ^C/^C ratio in atmospheric carbon dioxide at the time the carbon dioxide is fixed and also reflects the precise metabolic pathway. Regional variations also occur. Petroleum, C3 plants (the broadleaf), C₄ plants (the grasses), and marine carbonates all show significant differences in ^JC/¹²C and the corresponding δ ^JC values.

Furthermore, lipid matter of C3 and C₄ plants analyze differently than materials derived from the carbohydrate components of the same plants as a

consequence of the metabolic pathway. Within the precision of measurement, 3C shows large variations due to isotopic fractionation effects, the most significant of which for the instant invention is the photosynthetic mechanism. The major cause of differences in the carbon isotope ratio in plants is closely associated with differences in the pathway of photosynthetic carbon metabolism in the plants, particularly the reaction occurring during the primary

carboxylation, i.e., the initial fixation of atmospheric CO2. Two large classes of vegetation are those that incorporate the "C3" (or Calvin-Benson) photosynthetic cycle and those that incorporate the "C₄" (or Hatch-Slack) photosynthetic cycle. C3 plants, such as hardwoods and conifers, are dominant in the temperate climate zones. In C3 plants, the primary CO2 fixation or carboxylation reaction involves the enzyme ribulose-1 ,5-diphosphate carboxylase and the first stable CL6091 USNA

product is a 3-carbon compound. C₄ plants, on the other hand, Include such plants as tropical grasses, corn and sugar cane, in C₄ plants, an additional carboxy!ation reaction involving another enzyme, phosphenoi-pyruvate carboxylase, is the primary carboxylation reaction. The first stable carbon compound is a 4-carbon acid, which is subsequently decarboxyiated. The CO2 thus released is refixed by the C3 cycle.

Both C₄ and C3 plants exhibit a range of ^jC/¹²C isotopic ratios, but typical vaiues are ca. -10 to -14 per mil (C₄) and -21 to -26 per mil (C3) (Weber et ai., J. Aqnc. Food Chem.. 45, 2042 (1997)). Coal and petroleum fall generally in this latter range. The ¹³C measurement scale was originally defined by a zero set by pee dee belemnite (PDB) limestone, where values are given in parts per thousand deviations from this material. The "5¹³C" vaiues are in parts per thousand (per mil), abbreviated %o, and are calculated as follows:

5 ³C ≡ (¹³C/ ²C)sampie - (¹³C/ ²C)standard x 1000%o

(¹ C/¹²C)standard

Since the PDB reference material (RM) has been exhausted, a series of alternative R s have been developed in cooperation with the IAEA, USGS, N!ST, and other selected international isotope laboratories. Notations for the per mil deviations from PDB is 5¹³C. Measurements are made on CO2 by high precision stable ratio mass spectrometry (IRMS) on molecular ions of masses 44, 45 and 46.

Biologically-derived 1 ,3-propanedioI, and compositions comprising biologically-derived 1 ,3-propanediol, therefore, may be completely distinguished from their petrochemical derived counterparts on the basis of ⁴C (f^) and dual carbon-isotopic fingerprinting, indicating new compositions of matter. The ability to distinguish these products is beneficial in tracking these materials in commerce. For example, products comprising both "new" and "old" carbon isotope profiles may be distinguished from products made only of "old" materials. Hence, the instant materials may be followed in commerce on the basis of their unique profile and for the purposes of defining competition, for determining shelf life, and especially for assessing environmental impact. CL6091 USNA

Preferably the 1 ,3-propanediol used as the reactant or as a component of the reactant will have a purity of greater than about 99%, and more preferably greater than about 99.9%, by weight as determined by gas chromatographic analysis. The purified 1 ,3-propanediol preferably has the following characteristics:

(1 ) an ultraviolet absorption at 220 nm of less than about 0.20(3, and at 250 nm of less than about 0.075, and at 275 nm of less than about 0.075; and/or

(2) a composition having CIELAB L*a*b* "b*" color value of less than about 0.15 (ASTM D6290), and an absorbance at 270 nm of less than about

0.075; and/or

(3) a peroxide composition of less than about 10 ppm; and/or

(4) a concentration of total organic impurities (organic compounds other than 1 ,3-propanediol) of less than about 400 ppm, more preferably less than about 300 ppm, and still more preferably less than about 150 ppm, as measured by gas chromatography.

The starting material for making P03G will depend on the desired P03G, availability of starting materials, catalysts, equipment, etc., and comprises "1 ,3-propanediol reactant." By "1 ,3-propanediol reactant" is meant 1 ,3-propanediol, and oligomers and prepolymers of 1 ,3-propanediol preferably having a degree of polymerization of 2 to 9, and mixtures thereof. In some instances, it may be desirable to use up to 10% or more of low molecular weight oligomers where they are available. Thus, preferably the starting material comprises 1 ,3-propanediol and the dimer and trimer thereof. A particularly preferred starting material is comprised of about 90% by weight or more 1 ,3-propanediol, and more preferably 99% by weight or more

1 ,3-propanediol, based on the weight of the 1 ,3-propanediol reactant.

As indicated above, poly(trimethylene ether) glycol may contain lesser amounts of other polyalkyiene ether repeating units in addition to the CL6091 USNA

trimethy!ene ether units. The monomers for use in preparing poiytrirnethylene ether glycol can, therefore, contain up to 50% by weight (preferably about 20 wt% or less, more preferably about 10 wt% or less, and still more preferably about 2 wt% or less), of comonomer polyois in addition to the 1 ,3-propanediol reactant. Comonomer polyois that are suitable for use in the process include aliphatic diols, for example, ethylene glycol, 1 ,6-hexanediol, 1 ,7-heptanedioi, 1 ,8-octanediol, 1 ,9-nonanediol, 1 ,10-decanedioi, 1 ,12-dodecanedioL

3, 3,4,4,5, 5-hexafluro-1 ,5-pentanediol, 2,2,3,3,4,4,5,5-octafiuoro-l ,6-hexanedioI, and 3,3,4,4,5,5,6,8,7,7,8,8,9,9,10,10-hexadecafluoro-1 ,12-dodecanediol;

cycioaliphatic diols, for example, 1 ,4~cyc!ohexanediol,

1 ,4-cyclohexanedimethanol and isosorbide; and poiyhydroxy compounds, for example, glycerol, trimethyloipropane, and pentaerythritoi. A preferred group of comonomer diols is selected from the group consisting of ethylene glycol, 2-methyl-1 ,3-propanediol, 2,2-dimethyI-1 ,3-propanedioi, 2,2-diethyl-1 ,3- propanediol, 2-ethy!-2-(hydroxymethy!)-1 ,3-propanedioi, Ce^■■■■ Cio diols (such as 1 ,6-hexanedioi, 1 ,8-octanedioi and 1 , 10-decanedioi) and isosorbide, and mixtures thereof. A particularly preferred dioi other than 1 ,3-propanediol is ethylene glycol, and Ce - C-io diols can be particularly useful as well.

One preferred poiy(trimethylene ether) glycol containing comonomer is poly(trimethylene-ethyiene ether) glycol. Preferred poly(trimethylene-ethyiene ether) glycols are prepared by acid catalyzed polycondensation of from 50 to about 99 mole% (preferably from about 60 to about 98 mo!e%, and more preferably from about 70 to about 98 moie%) 1 ,3-propanedioi, and from about 50 to about 1 mole% (preferably from about 40 to about 2 mole%, and more preferably from about 30 to about 2 moie%) ethylene glycol.

The preferred poiy(trimethylene ether) glycol for use in the invention has an Mn (number average molecular weight) of at least about 134, more preferably at least about 1000, and still more preferably at least about 2000. The Mn is preferably less than about 5000, more preferably less than about 4000, and still more preferably less than about 3500. Blends of

poly(trimethylene ether) glycols can also be used. For example, the CL6091 USNA

poly(trimethylene ether) glycol can comprise a blend of a higher and a lower molecular weight poiy(trimethyiene ether) glycol, preferably wherein the higher molecular weight poiy(trimethy!ene ether) glycol has a number average molecular weight of from about 1000 to about 5000, and the lower molecular weight poly(trimethylene ether) glycol has a number average molecular weight of from about 200 to about 950. The Mn of the blended poly{trimethyiene ether) glycol will preferably still be in the ranges mentioned above.

Polyitrimethyiene ether) glycols preferred for use herein are typically polydisperse having a polydispersity (i.e. w/ n) of preferably from about 1.0 to about 2.2, more preferably from about 1 .2 to about 2.2, and still more preferably from about 1 .5 to about 2.1 . The polydispersity can be adjusted by using blends of poly(trimethyiene ether) glycols.

Poiy(trimethyiene ether) glycols for use in the present disclosure preferably has a color value of less than about 100 APHA, and more preferably less than about 50 APHA.

Polyitrimethyiene ether) glycol can be made via a number of processes known in the art.

Poiy(trimethylene ether) glycol esters are preferably prepared by polycondensation of hydroxy! groups-containing monomers (monomers containing 2 or more hydroxyl groups) predominantly comprising 1 ,3- propanediol to form a poiy(trimethyiene ether) glycol, followed by esterification with a monocarboxylic acid, as disclosed in U.S. Application Serial No.

1 1/593,954, filed November 7, 2006, entitled TOLYTRI METHYLENE ETHER GLYCOL ESTERS". Preferred monocarboxylic acids used in esterification are: propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, peiargonic acid, capric acid, lauric acid, palmitic acid, oleic acid and stearic acid, benzoic acid and 2-ethyl-hexanoic acid.

Alternatively the poly(trimethylene ether) glycol esters can be prepared by (trans)esterfication of trimetbylene ether glycol oligomers having a degree of polymerization from 2 to 8 with a monocarboxylic acid or its ester. CL6091 USNA

The po!y(trimethylene ether) glycol esters can be used as plasticizers for a variety of polymers, herein also referred to as "base polymers". Although any ester can be used, including copolyether esters, particularly preferred ones for the present disclosure include po!y(trimetby!ene ether) glycol 2-ethyihexanoate. Other copolyether esters include poly(trimethy!ene ether) glycol laureate, poly(trimethylene ether) glycol oleate, and poiy(trimethyiene ether) glycol stearate. Generally, the ester is added to the base polymer in an effective amount. As used herein, "effective amount" means the amount of piasticizer that provides improved physical properties to the base polymer (generally, increased flexibility, workability) so that the plasticized base polymer exhibits improved performance in the desired end use. Generally, the piasticizer is added to the base polymer in amounts of about 10 percent by weight or less, although it can be added in amounts up to about 40 percent by weight. When added at above about 10 percent by weight, the esters can function in such a way as to be termed "flow aids" in addition to to as plasticizers. The esters can be used as plasticizers (and flow aids) for a variety of base polymers. The base polymers for which the presently disclosed esters can be used as plasticizers include, for example, polyesters, polyamides, poiyurethanes, polyolefins, polyvinyl chloride (PVC) and polyvinyl butyrai (PVB), and mixtures thereof. The piasticizer can be added to the base polymer using any convenient method known to the skilled artisan. Generally, the piasticizer is mixed with the base polymer in a mixer and the temperature is elevated to between 150 and 250 °C, although this temperature is dependent on the melt temperatures of base polymer and piasticizer used. Alternatively to melt processing, solvent or aqueous (wet) slurry processes can be used to add piasticizer to the polymer.

After the base polymer and piasticizer are mixed (generally, 15 minutes to 6(3 minutes, but the time can vary depending upon the nature and properties of the materials mixed) the mixture is cooled. While any cooling method can be used, liquid nitrogen is generally used so that the plasticizer-base polymer mixture is cooled to a temperature where it can be ground. CL6091 USNA

Any grinding procedure can be used, and the material is generally ground to particle sizes of between about 0.1 and 10 mm, or any size that will allow further processing. Once the material is ground, then it is dried at a slightly elevated temperature (generally around 80 °C) under an inert atmosphere (generally nitrogen gas). The dried, ground material can then be further processed to form the desired product. The processing can take place in an extruder, or press mold, for example.

The amount of poly(trimethylene ether) glycol ester added to a base polymer is in the range from 1 to 40% by weight based on the total combined weight of the base polymer and plasticizer. In preferred embodiments, about 2 to 30% by weight of polyitrimethylene ether) glycol ester is used.

The poly(trimethylene ether) glycol esters can be blended with other known ester plasticizers such as, for example, synthetic and natural esters. Natural esters include vegetable based triglyceride oils such as soybean, sunflower, rapeseed, palm, canoia, and castor oils. Preferred vegetable oils include castor oil, high oleic soybean and high oleic sunflower oils.

After the material has been processed, the composition is tested by a variety of methods, including tensile and tear strengths at given temperatures, burst strengths, burning characteristics, electrical properties, dielectric properties, surface characteristics (feel or "hand" and resistance to soiling and staining), and pliability at given temperatures (Durometer hardness and bending properties). Various test methods are commonly used, such as AST No. D638. in another embodiment, there is provided a polymer composition comprising an effective amount of plasticizer in an aliphatic po!yamide base polymer, wherein the plasticizer comprises an aromatic ester of

polyitrimethylene ether) glycol.

Poiyamides (abbreviated PA), also referred to as nylons, are

condensation products of one or more dicarboxylic acids and one or more diamines, and/or one or more aminocarboxyiic acids such as 1 1 CL6091 USNA

aminododecanoic acid, and/or ring opening polymerization products of one or more cyclic lactams such as caprolactam and laurolactam. Suitable po!yamides may be fully aliphatic or semi-aromatic.

Po!yamides from single reactants such as lactams or amino acids, referred to as AB type poiyamides are disclosed in Nylon Plastics (edited by Melvin L. Kohan, 1973, John Wiley and Sons, Inc.) and include nylon 6, nylon 1 1 , nylon 12. Poiyamides prepared from more than one lactam or amino acid include nylon 612.

Other well-known poiyamides include those prepared from condensation of diamines and diacids, referred to as AABB type poiyamides (including nylon 86, nylon 610 and nylon 612), as well as from a combination of lactams, diamines and diacids such as nylon 6/66, nylon 6/610, nylon 6/66/610, nylon 66/610, or combinations of two or more thereof.

Poiyamides suitable for use as base polymers are aliphatic. By

"aliphatic" it is meant poiyamides that are formed from aliphatic and alicyciic monomers such as diamines, dicarboxyiic acids, lactams, aminocarboxylic acids, and their reactive equivalents. In this context, the term "aliphatic polyamide" also refers to copolymers derived from two or more such monomers and blends of two or more fully aliphatic poiyamides. Linear, branched, and cyclic monomers may be used. Aliphatic poiyamides, as defined herein, can be a mix of aliphatic and aromatic dicarboxyiic acids. In a non-limiting example, a portion of the aliphatic adipic acid can be replaced with terephthaiic acid, isophthaiic acid, furan dicarboxyiic acid or trimeilitate ester.

Carboxylic acid monomers comprised in the aliphatic poiyamides include, but are not limited to aliphatic dicarboxyiic acids, such as for example succinic acid (04), adipic acid (C6), pimelic acid (07), suberic acid (08), azelaic acid (09), decanedioic acid (010) and dodecanedioic acid (C12). Diamines can be chosen among diamines with four or more carbon atoms, including but not limited to tetramethylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethyiene diamine, 2- CL6091 USNA

methylpentamethylene diamine, 2 elbyltelramethylene diamine, 2- methyloctamethylenediamine, trimethyihexamethyienediamine and/or mixtures thereof.

Preferred poiyamides disclosed herein are homopolymers or copolymers wherein the term copolymer refers to poiyamides that have two or more amide and/or diamide molecular repeat units. The homopolymers and copolymers are identified by their respective repeat units. For copolymers disclosed herein, the repeat units are listed in decreasing order of mole % repeat units present in the copolymer. The naming system that has developed around the naming of poiyamides (nylons) is well-known to one of ordinary skill in the art, and such naming protocols are observed herein, unless the context indicates that the standard naming system is not being followed. For the avoidance of doubt:

"H D"as used herein refers to bexametnylene diamine ; "AA" as used herein refers to Adipic acid; "TMD" as used herein refers to 1 ,4-tetramethylene diamine. in one embodiment, the aliphatic poiyamide base polymer comprises nylon 8, nylon 66, nylon 610, nylon 1010, nylon 612, nylon 1 1 , nylon 12, or mixtures thereof. In another embodiment, the aliphatic poiyamide base polymer comprises nylon 6 or nylon 12. For purposes herein, "aromatic" refers to any compound that having an aromatic hydrocarbon radical, whether or not said radical has a substituent or is unsubstituted. Common examples of aromatic hydrocarbons include benzene; biphenyl; terphenyl; naphthalene; phenyl naphthalene; para-, ortho- or metahydroxybenzoic acid; trimeiiitic; and naphfhylbenzene. In one embodiment the aromatic compound can be a phenolic compound, in another embodiment the aromatic ester of poiy(trimethyiene ether) glycol can be a benzoate ester; a (ortho-, meta-, or parahydroxybenzoate ester; a phfhalate ester; a terephthlate ester; or a trimeliitate ester.

The aromatic esters of poiy(trimethylene ether) glycol can comprise monoesters, diesters or mixture of mono and diesters. The polarity of the CL6091 USNA

aromatic ester of poly(trimethylene ether) glycol can be controlled by the degree of aromatic ester groups in the molecuie and length of the polymer chain. A high degree of diesters in the aromatic esters of po!ytrimethy!ene ether glycol is preferred for relatively non-polar polyamides such as PA1 1 and PA12, and a low degree of diesters is preferred for polar polyamides such as PA8 and PA68. The number average molecular weight (Mn) of the aromatic esters of poly(trimethylene ether) glycol is typically in the range from about 250 to about 1000, or from about 400 to about 800.

The plasticizer comprising the aromatic esters of poly(trimethylene ether) glycol can be blended with other plasticizers, such as, for example, synthetic and natural esters. Natural esters include vegetable based triglyceride oils such as soybean, sunflower, rapeseed, palm, canoia, and castor oils. Preferred vegetable oils include epoxidized vegetable oils such as soybean oil, sunflower oil, rapeseed oil, palm oil, canoia oil, and castor oil. Any suitable method known in the art may be used for mixing polymeric ingredients and non-polymeric ingredients described herein. For example, polymeric ingredients and non-polymeric ingredients may be fed into a melt mixer, such as single screw extruder or twin screw extruder, agitator, single screw or twin screw kneader, or Banbury mixer, and the addition step may be addition of all ingredients at once or gradual addition in batches. When the polymeric ingredient and non-polymeric ingredient are gradually added in batches, a part of the polymeric ingredients and/or non-polymeric ingredients is first added, and then is melt-mixed with the remaining polymeric ingredients and non-polymeric ingredients that are subsequently added, until an adequately mixed composition is obtained.

The specific use or application can determine what amount is effective. Other considerations may be used to determine what amount may be included in a plasticized mixture of the present invention, including cost. However, the effectiveness of a plasticizer of the present invention is determined by the measurement of physical properties of the base polymer and the plasticized polymer. In the present invention an effective amount can be any amount in CL6091 USNA

the range of from about 1 to about 40 wt%. Alternatively an effective amount can be from about 5 to about 40 wt%, or from about 10 to about 20 wt%, or from about 10 to about 15 wt%, based on the weight of the base polymer,

Surprisingly, it has been found that poiyamide compositions such as Nylon 6, when plasticized with a plasticizer of the present invention, can provide resistance to stress cracking of an article that has been exposed to ZnC for 7 days or more and which is formed from said plasticized composition. In addition said plasticized composition demonstrates a moisture barrier to prevent absorption of water by the polymer composition, and also good flexibility of the plasticized polymer.

Further, blended plasticizer compositions can be suitable for use herein, wherein blends of PPDB and polyproplyene diol provide advantages when used with polyamides such as Nylon 6, for example.

The plasticized polymer compositions may also comprise other additives commonly used in the art, such as heat stabilizers, antioxidants, antistatic agents, lubricants, colorants and pigments.

The aliphatic poiyamide base polymer or plasticized polymer

composition can also be a blend comprising an aliphatic poiyamide with other polymers such as other polyamides, (meth)acryiates polymers and/or ionomeric polymers.

Particularly suitable ionomeric polymers contain in-chain copoiymerized units of ethylene, copoiymerized units of an α,β-unsaturated C3-C8

monocarboxylic acid and copoiymerized units of at least one efhylenicaiiy unsaturated dicarboxyiic acid comonomer selected from C4 -C8 unsaturated acids having at least two carboxylic acid groups, cyclic anhydrides of C4-C8 unsaturated acids having at least two carboxylic acid groups, and monoesters (wherein one carboxyl group of the dicarboxyiic moiety may be esterified and the other is a carboxylic acid) of C4 -C8 unsaturated acids having at least two carboxylic acid groups; at least partially neutralized to salts comprising alkali metal, transition metal, or alkaline earth metal cations, such as lithium, sodium, CL6091 USNA

potassium, magnesium, calcium, or zinc, or a combination of such cations. The monocarboxylic acid can include acrylic acid or methacrylic acid; and the dicarboxylic acid or derivative thereof can include ma!eic acid, fumaric acid, itaconic acid, maieic anhydride, fumaric anhydride, itaconic anhydride, one or more C1 -4 aikyl half ester of maleic acid, one or more C1 -4 alkyl half ester offumaric acid, one or more C1 -4 alky! half ester of itaconic acid, or

combinations of two or more thereof. One particularly suitable ionomeric polymer is Surlyn® (E.I. DuPont de Nemours & Co.).

The ionomeric copolymer can be included in an amount of less than about 50 wt% of the weight of the unplasticized polymer blend. Alternatively, the ionomeric copolymer can be included in an amount of 40 wt% or less.

The polymer composition, optionally, comprises 0 to 20 weight percent of one or more polymer impact modifiers. The polymer impact modifiers comprise a reactive functional group and/or a metal salt of a carboxylic acid.

In one embodiment the polymer composition can comprise 2 to 20 weight percent, and preferably 5 to 12 weight percent polymer impact modifiers. In another embodiment the polymer impact modifiers are selected from the group consisting of: a copolymer of ethylene, giycidyi (meth)acrylate, and optionally one or more (mefh)acrylate esters; an efhylene/a-o!efin or ethylene/o-olefin/diene copolymer grafted with an unsaturated carboxylic anhydride; a copolymer of ethylene, 2~isocyanatoethyl (meth)acryiate, and optionally one or more (mefh)acryiate esters; and a copolymer of ethylene and acrylic acid reacted with a Zn, Li, Mg or Mn compound to form the

corresponding ionomer.

Also described herein is a process for producing a p!asticized polymer, comprising: (a) providing an aliphatic polyamide base polymer; (b) adding to the base polymer an effective amount of a plasticizer, wherein the plasticizer comprises an aromatic ester of po!yftrimethy!ene ether) glycol; (c) processing the base polymer and plasticizer to form a mixture; and (d) cooling the mixture and optionally grinding the mixture to produce particles. The aliphatic base polymer and aromatic ester are as described above. CL6091 USNA

The process may also comprise melt processing at a temperature from 20 to 40 °C above the melt temperature of the base polymer, and may also comprise forming an article from the particles by extrusion molding, injection molding, or press molding, Also described herein are shaped articles comprising the polymer composition described above. Examples of shaped articles are films, fibers, or laminates, automotive parts or engine parts or electrical/electronic parts. By "shaping", it is meant any shaping technique, such as for example extrusion, injection molding, extrusion molding, thermoform molding, compression molding, extrusion blow molding or biaxial stretching blowing parisons (injection stretch blow molding), melt spinning, profile extrusion, heat molding or blow molding. Preferably, the article is shaped by injection molding or blow molding. The molded or extruded shaped articles disclosed herein may have application in automotive and other components that meet one or more of the following requirements: high chemical resistance to polar chemicals such as such as zinc chloride and calcium chloride, high impact requirements; resistance to oil and fuel environment; resistance to chemical agents such as coolants; low permeability to fuels and gases, e.g. carbon dioxide. Specific extruded or molded shaped articles are selected from the group consisting of pipes for transporting liquids and gases, inner linings for pipes, fuel lines, air break tubes, coolant pipes, air ducts, pneumatic tubes, hydraulic houses, cable covers, cable ties, connectors, canisters, and push-pull cables.

EXAMPLES

The present invention is further illustrated in the following examples. These examples, while indicating preferred embodiments of the invention, are presented by way of illustration only. From the above discussion and these examples, one skilled in the art can ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can CL6091 USNA

make various changes and modifications of the invention to adapt it to various usages and conditions.

AH parts, percentages, etc., are by weight unless otherwise indicated.

Example 1

This example illustrates the synthesis of a 2-ethylhexanoate ester of polyfrimefhylene ether glycol.

1 ,3-propanediol (2.4 kg, 31 .5 moles) was charged into a 5 L flask fitted with a stirrer, a condenser and an inlet for nitrogen. The liquid in the flask was flushed with dry nitrogen for 30 minutes at room temperature and then heated to 170X while being stirred at 120 rpm. When the temperature reached 170°C, 12.6 g (0.5 wt%) of concentrated sulfuric acid was added. The reaction was allowed to proceed at 170°C for 3 hours, and then the temperature was raised to 180°C and held at 180°C for 135 minutes. A total of 435 mL of distillate was collected. The reaction mixture was cooled, and then 2.24 kg (14.6 moles) of 2-ethyihexanoic acid (99%) was added. The reaction temperature was then raised to 160°C under nitrogen flow with continuous agitation at 180 rpm and maintained at that temperature for 6 hours. During this period an additional 305 mL of distillate water was collected. Heating and agitation were stopped and the reaction mixture was allowed to settle. The product was decanted from about 5 g of a lower, immiscible by-product phase. NMR analysis of the by-product phase confirmed that no carboxylic acid esters were present.

2.0 kg of the polytrimethyiene ether glycol ester product was mixed with 0.5 kg of water, and then the resulting mixture was heated at 95°C for 6 hours. The aqueous phase was separated from the polymer phase, and then the polymer phase was washed twice with 2.0 kg of water. The resulting product was heated at 12QX at 200 mTorr to remove voiatiles (255 g).

The resulting ester product was analyzed using proton NMR. No peaks associated with sulfate esters and unreacfed 2-ethylhexanoic acid were found. CL6091 USNA

The calculated number average molecular weight was found to be 525. There was no sulfur detected in the polymer when analyzed using WDXRF

spectroscopy method.

Example 2 In this example the ester obtained in Example 1 was fractionated into several fractions of differing molecular weights.

The product obtained in Example 1 was passed through a short path distillation apparatus under conditions of 160°C, 130 mTorr and a flow rate of 7 mL/minute. Two fractions were collected. The volatile fraction had a number average molecular weight of 370. The non-volatile fraction was once again passed through the short path distillation unit at 180°C, 1 10 mTorr and a flow rate of 4.5 mL. The volatile fraction from this run had a number average molecular weight of 460, corresponding largely to trimer and tetramer esters.

Example 3 This example illustrates the preparation of the 2-etbylbexanoate ester of polytrimethylene ether glycol of higher molecular weight than that prepared in Example 1 .

The raw materials and procedure were the same as those described in Example 1 , with the exceptions that the amount of sulfuric acid was increased to 14.9 g (0.6 wt%) and the polymerization time was increased from 315 to 525 minutes. A total of 545.3 mL of distillate was collected during polymerization. The esterification was carried out by adding 943.8 g (6.5 moles) of

2-ethyihexanoic acid as described in Example 1 . The distillate collected during esterification was 1 13 mL. After hydrolysis, the product was purified by neutralizing free sulfuric acid remaining in the product. The neutralization was carried out as follows. The product (1516 g) was transferred to a reaction flask, 0.15 g of Ca(OH)₂ in 15 mL of deionized water was added, and the mixture was heated to 70°C while stirring under nitrogen stream. The neutralization was continued for 3 hours and CL6091 USNA

then the product was dried at 1 10°C for 2 hours under reduced pressure and filtered to remove solids. After filtration, the product was analyzed and found to have a number average molecular weight of 870. Example 4

This example illustrates the synthesis of a 2-ethylhexanoate ester of a poly(trimethylene-co-ethylene ether) glycol ester.

1 ,3-propanedio! (0.762 kg, 10 moles) and ethylene glycol (0.268 kg, 4.32 moles) were charged into a 5 L flask fitted with a stirrer, a condenser and an inlet for nitrogen. The liquid in the flask was flushed with dry nitrogen for 30 minutes at room temperature and then heated to 170°C while being stirred at 120 rpm. When the temperature reached 170°C, concentrated sulfuric acid

(5.2 g) was added to the reaction mixture. The reaction was allowed to proceed at 170°C for 3 hours, and then the temperature was raised to 180°C and held at 180°C for 135 minutes. A total of 258 mL of distillate was collected. The reaction mixture was cooled, and then 0.5 kg kg (3.4 moles) of 2-ethylhexanoic acid (99%) was added. The reaction temperature was then raised to 160°C under nitrogen flow with continuous agitation at 180 rpm and maintained at that temperature for 6 hours. During this period an additional 63 mL of distillate water was collected. The product was hydrolyzed and purified as described in Example 1 .

The resulting ester product was analyzed using proton N R. No peaks associated with sulfate esters and un-reacted 2-ethyihexanoic acid were found. The calculated number average molecular weight was found to be 620. There was no sulfur defected in the polymer when analyzed using WDXRF

spectroscopy method.

Examples 5-10 CL6091 USNA

The following examples illustrate plasticization of polyvinyl butyra! (PVB) polymer with poly(trimethylene ether) glycol esters.

About 50 g of wet PVB (about 40% water) was mixed with about 150 g of hot water (38 °C) in a glass kettle. About 13 g of the poly(trimethylene ether ) glycol-2-ethyi hexanoate was charged to the kettle. Plasticization was carried out for 4 hours at 38 °C and at 650 rpm. The piasticized PVB was washed with water and oven dried for 16 hours at 60 °C. The piasticized polymers were press molded (moid size 220 mm x 150 mm) in a Teflon® coated aluminum moid at 220 °C. Physical measurements were run on the test bars (ASTM D1708-06a) on an instron Corporation Tensile Tester, Model no. 1 125 (instron Corp., Norwood MA) at 23 °C and 50% RH. Table 1 lists the properties of piasticized PVB.

Table 1 . Mechanical ro erties of iasticized PVB ol mer

Example 9

The experiment described in Example 5 was repeated with an amount 50% less of po!y(trimethylene ether) glycol 2-ethyihexanoate and the results are reported below.

CL6091 USNA

Example 10 42 g of PVB dried resin was blended with 18 g of polyffrimethylene ether) giycol-2-ethyl hexanoate using an industrial mixer (C. W. Brabender Instruments Inc. NJ) for about 6 minutes. The mixer speed was 40 rpm and the mixer temperature was 210 °C. After mixing the polymer was cooled, then liquid 2 was used in the grinding process (Thomas industrial grinder, Thomas, Philadelphia, PA) to achieve 1 -5 mm particle size of polymer. The ground polymer was dried at 80 °C in vacuum under 2 blanket. The polymers were press molded (mold size 220 mm x 150 mm) in a Teflon© coated aluminum mold at 220°C. Physical measurements were run on the test bars (ASTM D1708-08a) on an instron Corporation Tensile Tester, Model no. 1 125 (instron Corp., Norwood MA).

Example 1 1

The synthesis of poly(trimethylene ether) glycol benzoate (polyl ,3- propanedioi benzoate) was carried out in two different routes as described below:

Method A: Polycondensation of 1 ,3-propanediol followed by esterification with benzoic acid

Biosourcedl ,3-propanediol (Bio-PDO 4.08 kg, 53.6 moles, DuPont and Tate & Lyle Bioproducfs) was charged into a 5 L flask fitted with a stirrer, a CL6091 USNA

condenser and an inlet for nitrogen. The liquid in the flask was flushed with dry- nitrogen for 1 h at room temperature. 33.2 g of concentrated sulfuric acid and 16.98 g of sodium carbonate solution having 1 .74 g of sodium carbonate dissolved in 15.25 g of deionized water were added. The reaction mixture was heated to 166° C while being stirred at 120 rpm for 8 hours. A total of 720 mL of distillate (water) was collected during the reaction. The reaction mixture was cooled, and 0.462 kg (3.8 moles) of benzoic acid was added to 0.5 Kg product obtained. The reaction temperature was then raised to 120° C under nitrogen flow with continuous agitation at 180 rpm and maintained at that temperature for 7 hours. The reaction mixture was cooled, 0.5 kg of deionized water was added, and then the resulting mixture was heated at 95° C for 2 hours. The reaction mixture was cooled to 60° C and 270 g of 3.33 wt % sodium carbonate solution was added and the mixture was agitated at 60° C for 30 min. The mixture was transferred to separating funnel and the aqueous layer was removed after separation. The product was again washed with 500 mL of deionized water. The obtained product was dried using rotary evaporator at about 85° C and 200 mTorr pressure.

The dried product was characterized by proton MR. The product had a number average molecular weight (Mn) of 445 with a mixture of 75.9 mole% diester and 24.1 mo!e% of monoester.

Method B : Transesterfication of poiyitrimethylene ether) glycol with

methy!benozoate

Poiy(trimethylene ether) glycol, ( n 255, 0.495 kg, 1 .94 moles), prepared as described in WO2012148849, methylbenzoate (0.534 Kg, 3.93 moles), sodium methoxide (10.01 g, 0.97 wt %) were charged into a 2 L flask fitted with a stirrer, a Dean Stark trap and an inlet for nitrogen. The liquid in the flask was flushed with dry nitrogen for 0.5 h at room temperature. The reaction mixture was heated to 100°C while being stirred. After 1 h the reaction temperature was incrementally raised to 180° C in 3 h and the reaction was allowed to proceed at 180°C for 1 .5 hours. A total of 72 mL of distillate CL6091 USNA

(methanol) was collected. Then the reaction mixture was cooled and filtered using Whatman™ #42 filter paper. The filtered product was mixed with 500 mL of deionized water and heated at 70° C for 30 min. The mixture was transferred to separating funnel and organic product was collected. Unreacted

methylbenzoate in the product was removed by distilling at 150 °C 200 rnTorr pressure.

The product was characterized by NMR. The product had a number average molecular weight (Mn) of 458 with a mixture of 81 .8 mole% diester and 18.2 moie% monoester.

exuberant

Example 12

Synthesis of Poly(trimethylene ether) glycol ethyl 2-hydroxybenzoate

Poiy(trimethylene ether) glycol (Mn 255, 0.295 kg, 1 .15 moles), ethylsalicylate (0.35Kg, 2.1 moles), sodium methoxide (6.5 g, 1 wt %) were charged into a 2 L flask fitted with a stirrer, a dean stark trap and an inlet for nitrogen. The liquid in the flask was flushed with dry nitrogen for 0.5 h at room temperature. The reaction mixture was heated to 135° C while being stirred for an hour. The reaction temperature was incrementally raised to 180° C in 3 h and the reaction was allowed to proceed at 18(3° C for 1 h. A total of 92 mL of distillate was collected. The obtained product was mixed with 500 mL of deionized water at 50° C for 30 min. The mixture was transferred to a separating funnel and the organic product was collected. The product was again mixed deionized water at room temperature and transferred to separating funnel. The organic product was collected and unreacted ethylsalicylate was distilled at 150° C 200 mTorr pressure for 3 h.

The product was characterized by NMR. The product had a number average molecular weight of 494 with a mixture of 85.7 moie% diester and 14.3 mole% monoester. CL6091 USNA

Example 13

Various poiyamide samples were prepared containing either no piasticizer or various plasticizers: poly(1 ,2-propylene glycol) dibenzoate (Aldrich, Mn 400), the benzoate ester from Method A of Example 1 , and the 2- ethylhexanoate ester from Example 1 ). Samples were compounded using a 26 mm Coperion twin-screw extruder. Extruder barrel temperatures were controlled at 250° C. Poiyamide 12 (Rilsan AESNO, extrusion grade nylon 12 from Arkema) or nylon 6 (Ultramid B27, extrusion grade nylon 6 from BASF) were fed at barrel 5 followed by an intense mixing section in the extruder screw to melt the polymer, then by a vacuum vent at barrel 8 to remove any volatiles from the polymer melt. Extruder screw speed was controlled at 600 RPM, and the materials were extruded at 30 ib/hr (27.6 Ib/hr pellets; 2.4 ib/hr piasticizer). Liquid plasticizers were pumped into the extruder at barrel 12 (of 13 barrels total extruder length) at 8% of the polymer feed rate using an Isco syringe pump. The extruder was not vented after piasticizer addition, in order to keep the piasticizer in the melt stream. The melt stream was extruded through a 3/16" die, the strand was quenched in a water bath, and the cooled strand was cut into pellet form.

Pellets from the extrusion compounding step were dried in a desiccant drying oven at 80° C for about 16 hours and then molded into ASTM flex bars (5" x 0.5" x 0.125") on an Arburg 221 K 38 ton 1 .5 oz injection molding machine. Molding machine barrel temperature settings were controlled at about 270 degrees C, and the moid temperature was approximately 25° C. Moid cycle times and injection pressure were adjusted to accommodate the melt viscosity of the various samples.

Flex modulus testing:

Flexural modulus of ASTM flex bars that were injection molded was measured using test method ASTM D790 - 10 "Standard Test Methods for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical insulating Materials", procedure A. Span was 2", crosshead speed 0.057min, CL6091 USNA

and maximum strain was 2%. Nyion samples with no plasticizer were used as control samples with each set of experimental samples that were tested. The results are shown in Table 2 below. Where the results state "could not be injection molded", the plasticizer had apparently migrated to the surface of the pellets to the point that the material slipped on the feed screw and could not be fed into the molding cavity.

Table 2

The data in Table 2 demonstrates the effectiveness of benzoate ester of po!y(trimetby!ene ether) glycol in reducing the flex modulus of both nylon 6 and nylon 12 having different polarities, whereas the aliphatic ester could not be injection molded in either nylon, in contrast to benzoate ester of

polyitrimefhylene ether) glycol, the poly(1 ,2-propylene glycol) dibenzoate, an isomer, had significantly higher flex modulus in nylon 6 in spite of structural similarity.

Claims

CL6091 USNA CLAIMS What is claimed Is:

1 . A polymer composition, comprising an effective amount of plasticizer in an aliphatic polyamide base polymer, wherein the plasticizer comprises an aromatic ester of poly(trimethylene ether) glycol.

2. The polymer composition of Claim 1 , wherein the effective amount of plasticizer is from 1 to 40 % by weight based on the total weight of the base polymer.

3. The polymer composition of Claim 1 , wherein the aliphatic polyamide base polymer comprises nylon 6, nylon 66, nylon 610, nylon 1010, nylon 612, nylon 1 1 , nylon 12, or mixtures thereof.

4. The polymer composition of Claim 1 , wherein the aromatic ester of poly(trimethylene ether) glycol is a benzoate ester, hydro xybenzoate ester, phthalate ester, isophthalate ester, terephthlate ester, or trimeiiitate ester.

5. The polymer composition of Claim 1 , further comprising one or more additional natural or synthetic ester plasticizers.

6. The polymer composition of Claim 6, wherein the one or more additional natural esters is epoxidized oils selected from the group of soybean oil, sunflower oil, rapeseed oil, palm oil, canola oil, or castor oil. CL6091 USNA

7. The polymer composition of Claim 1 that has a flex modulus at least about 25% lower r than the flex modulus of the base polymer without the plasticizer, wherein the flex modulus is measured by ASTM D790-10 test method.

8, A process for producing a plasticized polymer, comprising:

(a) providing an aliphatic poiyamide base polymer;

(b) adding to the base polymer an effective amount of a plasticizer, wherein the plasticizer comprises an aromatic ester of polyftrimethylene ether) glycol;

(c) processing the base polymer and plasticizer to form a mixture; and

9. The process of Claim 8, further comprising forming an article from the particles by extrusion molding, injection molding, or press molding.

10. The process of Claim 8, wherein the effective amount of plasticizer is from 1 to 40% by weight based on the total weight of the base polymer.

1 1 . The process of Claim 8, wherein the aliphatic poiyamide base polymer comprises nylon 8, nylon 68, nylon 610, nylon 1010, nylon 812, nylon 1 1 . nylon

12. or mixtures thereof. CL6091 USNA

12. The process of Claim 8, wherein the aromatic ester of poly(trimethylene ether) glycol is a benzoate ester, hydroxybenzoate ester, phthalate ester, terephth!ate ester, or trimellitate ester,

13. The process of Claim 8, further comprising one or more additional natural or synthetic ester piasticizer.

14. The process of Claim 15, wherein the one or more additional natural ester piasticizer is epoxidized oils selected from the group of soybean oil, sunflower oil, rapeseed oil, palm oil, canola oil, or castor oil.

15. A shaped article comprising the polymer composition of Claim 1 .

16. The shaped article of Claim 15, wherein the effective amount of piasticizer is from 1 to 40 % by weight based on the total weight of the base polymer.

17. The shaped article of Claim 15, wherein the aliphatic polyamide base polymer comprises nylon 6, nylon 66, nylon 610, nylon 1010, nylon 612, nylon 1 1 , nylon 12, or mixtures thereof.

18. The shaped article of Claim 15, wherein the aromatic ester of poly(trimetbylene ether) glycol is a benzoate ester, hydroxybenzoate ester, phthalate ester, isophthalate ester, terephthlate ester, or trimeilitate ester.